Composition comprising a block polymer and a film-forming agent

Translation of description of equivalent WO 2004028487 A2

Composition comprising a block polymer and a film forming agent

The present invention relates to a cosmetic makeup or care of the skin, including the scalp, both of the human face and body, lips or nails of human beings, like hair, eyelashes, eyebrows or the nails, comprising a cosmetically acceptable medium containing a polymeric film sequence associated with another film former.

The composition may be a loose or compacted powder, a foundation, a blusher or eyeshadow, a concealer product, a blusher, a lipstick, a lip balm, a lip gloss, a pencil lip or eye, a mascara, an eyeliner, a nail varnish, a body makeup product or a skin coloring.

The known compositions have poor resistance over time, particularly poor color retention. This poor performance is characterized by a color change (color change or fading) generally following an interaction with the sebum and / or sweat secreted by the skin in the foundation case and shadow or interaction with saliva in the case of lipsticks. This requires the user to now disguised very often, which can be a waste of time. An improvement of the holding in particular the holding of lipsticks can be obtained by combining a volatile oil with a film forming polymer, such as silicone resins. However, the strength properties obtained remain below consumer expectations.

There remains a need for a cosmetic product which leads to a deposit on keratin materials, in particular a makeup, crisp.

The composition of the invention may in particular be a body makeup product, lips or integuments of humans especially having care properties and / or non-therapeutic treatment. It is especially a lipstick or a lip gloss, blush or eyeshadow, a tattoo product, a mascara, an eyeliner, a nail varnish, an artificial tanning product for the skin, a product coloring or hair care.

Surprisingly, the inventors have found that by combining a polymer particular sequence at a known film-forming agent is obtained cosmetic compositions which lead to deposit on keratin materials superior resistance to conventional compositions containing film-forming. More specifically, the invention relates to a cosmetic composition containing an organic liquid medium, at least one ethylene polymer film-forming linear block and at least one further film-forming agent.^{^} In particular, the invention relates to a cosmetic composition containing an organic liquid medium, at least one ethylene polymer film-forming linear block and at least one other film former soluble in the organic liquid medium. The invention has for another object a cosmetic composition containing an organic liquid medium, at least one ethylene polymer film-forming linear block and at least one other water soluble film forming agent.

The invention still further object a cosmetic composition containing an organic liquid medium, at least one ethylene polymer film-forming linear block and at least one aqueous dispersion of film-forming polymer particles. The invention still further object a cosmetic composition containing an organic liquid medium, at least one polymer forming linear ethylenic block and at least one non-aqueous dispersion of film-forming polymer particles.

The ethylenic polymer forming linear sequence is preferably non-elastomeric. The ethylene polymer forming linear sequence is advantageously free of styrene unit.

The invention also relates to a skin makeup process and / or the lips and / or superficial body growths which consists in applying to the skin and / or lips and / or integuments the composition as defined above.

The composition according to the invention can be applied to the skin as well as the face of the scalp and body, mucous membranes such as the lips, the inside of the lower eyelids and skin appendages such as the nails, eyelashes, hair , eyebrows or hair.

Preferably, the composition according to the invention is a leave-in composition.

The invention also relates to the cosmetic use of the composition defined above to improve the hold of the makeup on the skin and / or lips and / or integuments. In particular, in the case of a composition for coating the eyelashes or mascara, such a composition allows obtaining, after application to the eyelashes, a cosmetic film exhibiting good hold, in particular in water, in bathing or showers for example, friction, especially in the fingers and / or even to tears, sweat or sebum.

The invention finally relates to the use of a film forming agent in a composition containing a block polymer as described above to obtain a composition of good texture, easy to apply and leading on the lips and / or integuments a deposit good holding.

Polymer sequence:

The composition according to the present invention contains at least a polymer sequence. By "block polymer" means a polymer comprising at least two different blocks and preferably at least three distinct sequences.

According to one embodiment, the block polymer of the composition according to the invention is an ethylene polymer. The term "ethylenic polymer" means a polymer obtained by polymerizing monomers comprising an ethylenic unsaturation.

According to one embodiment, the block polymer of the composition according to the invention is a linear polymer. In contrast, a non-linear structure polymer is, for example, a polymer of branched structure, star, graft, or otherwise.

According to one embodiment, the block polymer of the composition according to the invention is a film forming polymer. By polymer "film" means a polymer capable, by itself or in the presence of an auxiliary film-forming agent, a continuous film that adheres to a support, especially to keratin materials.

According to one embodiment, the block polymer of the composition according to the invention is a non-elastomeric polymer.

"Non-elastomeric polymer" means a polymer which, when subjected to a stress intended to stretch it (for example by 30% relative to its initial length), does not return to a length substantially identical to its length initial when the stress. More specifically, "non-elastomeric polymer" denotes a polymer with an instantaneous recovery Ri <50% and a delayed recovery R_{2 hours} <70% after having undergone an elongation of 30%. Preferably, R, is <30%, and R_{2 hours} <50%.

More specifically, the non-elastomeric nature of the polymer is determined according to the following protocol:

a polymer film is prepared by pouring a solution of the polymer in a Teflon-coated mold and then drying for 7 days in a controlled environment at 23 ± 5 ° C and 50 ± 10% relative humidity.

We then obtain a film about 100 microns thick in which are cut rectangular specimens (for example a punch) of a width of 15 mm and a length of 80 mm.

It requires that sample to a tensile stress using a machine sold under the reference Zwick, under the same conditions of temperature and humidity for drying.

The specimens are pulled at a speed of 50 mm / min and the distance between the jaws is 50 mm, which corresponds to the initial length (l₀) Of the test piece.

It determines the instantaneous recovery R as follows:

- Is drawn the test piece by 30% (ε_myχ) that is to say, about 0.3 times its initial length (l₀)

- The stress is released by applying a return speed equal to the tensile speed, ie 50 mm / min and measuring the percentage of the residual elongation of the specimen, after returning to zero constraint (ει).

The% instantaneous recovery (R) is given by the following formula:

Ri = (ε_maχ- εi) / εm_ax) X 100

To determine the delayed recovery, the residual elongation is measured in percent specimen (ε_{2 hours}), 2 hours after returning to zero stress.

The% delayed recovery (R_{2 hours}) Is given by the following formula:

<img id="imgf000005_0001" he="5" wi="46" file="imgf000005_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Purely as a guide, a polymer according to one embodiment of the invention has an instantaneous recovery R of 10% and a delayed recovery R_{2 hours} 30%. .

According to another embodiment, the block polymer of the composition according to the invention does not comprise styrene unit. By polymer free of styrene units means a polymer comprising less than 10%, preferably less than 5%, preferably less than 2%, more preferably less than 1% by weight i) of styrene of the formula -CH unit (C₆H₅) -CH₂- Or ii) of substituted styrene units, for instance methylstyrene, chlorostyrene or chloromethylstyrene.

According to one embodiment, the block polymer of the composition according to the invention is derived from aliphatic ethylenic monomers. Aliphatic monomer means a monomer comprising no aromatic groups.

In one form. embodiment, the block polymer is an ethylenic polymer derived from aliphatic ethylenic monomers comprising a carbon-carbon double bond and at least one ester group -COO- or amide -CON-. The ester group may be linked to one of the two unsaturated carbons via the carbon atom or the oxygen atom. The amide group may be linked to one of the two unsaturated carbons via the carbon atom or the nitrogen atom.

According to one embodiment, the block polymer comprises at least one first block and at least one second sequence.

By "at least one block" means one or more sequences.

It was noted that in the above and following the terms "first" and "second" blocks do not in any way condition the order of the said sequences (or blocks) in the polymer structure.

According to one embodiment, the block polymer comprises at least one first block and at least one second block having glass transition temperatures (Tg).

In this implementation mode, the first and second blocks may be linked together via an intermediate segment having a glass transition temperature between the glass transition temperatures of the first and second sequences. According to one embodiment, the block polymer comprises at least one first block and at least one second block linked together via an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block .

Preferably, the intermediate block is derived essentially from constituent monomers of the first sequence and second sequence. By "substantially" means 85% at least, preferably at least 90%, more than 95% and even better still 100%. Advantageously, the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer.

According to one embodiment, the block polymer comprises at least one first block and at least one second sequence incompatible in the organic liquid medium of the composition of the invention.

"Mutually incompatible blocks with each other" means that the mixture formed from the polymer corresponding to the first block and the polymer corresponding to the second block is not miscible in the organic liquid majority by weight content in the organic liquid medium of the composition at room temperature (25 ° C) and atmospheric pressure (10⁵ Pa), for a content of the upper polymer blend or equal to 5% by weight, relative to the total weight of the mixture (polymers and major organic liquid), it being understood that: i) the said polymers are present in the mixture in a content such that the respective weight ratio ranges from 10/90 to 90/10, and ii) each of the polymers corresponding to the first and second blocks has an average molecular weight (weight or number) equal to that of the block polymer +/- 15%.

In the case where the organic liquid medium comprises a mixture of organic liquids, in the hypothesis of two or more liquids present in identical mass proportions, the said polymer mixture is immiscible in at least one of them.

In the case where the organic liquid medium comprises only one organic liquid, the latter is obviously the majority liquid by weight. By "organic liquid medium" means a medium containing at least one organic liquid, that is to say, at least one liquid organic compound at room temperature (25 ° C) and atmospheric pressure (10⁵ Pa). According to one embodiment, the majority liquid of the organic liquid medium is an oil (fat) volatile or nonvolatile. Preferably, the organic liquid is cosmetically acceptable (acceptable tolerance, toxicology and feel). The organic liquid medium is cosmetically acceptable, in that it is compatible with keratin materials, such as oils or organic solvents commonly used in cosmetic compositions.

According to one embodiment, the major liquid of the organic liquid medium is the polymerization solvent or one of the solvents of the block polymer as described below.

By polymerization solvent is meant a solvent or solvent mixture. The polymerization solvent may be chosen especially from ethyl acetate, butyl acetate, alcohols such as isopropanol and ethanol, aliphatic alkanes such as isododecane, and mixtures thereof. Preferably, the polymerization solvent is a mixture of butyl acetate and isopropanol, or isododecane.

In general, the block polymer may be incorporated into the composition at a high dry contents, typically greater than 10%, greater than 20% and more preferably greater than 30% and more preferably greater than 45% by weight relative to the total weight of the composition while being easy to formulate.

Preferably, the block polymer comprises no silicon atoms in its skeleton. The term "skeleton" means the main chain of the polymer, as opposed to the pendent side chains.

Preferably, the inventive polymer is not water soluble, i.e. the polymer is not soluble in water or in a mixture of water and of linear or branched lower monoalcohols containing from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, without pH modification, at an active material content of at least 1% by weight at room temperature (25 ° C).

According to one embodiment, the block polymer has a polydispersity index I of greater than 2. Advantageously, the block polymer used in the compositions according to the invention has a polydispersity index I of greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8 and better still greater than or equal to 2.8 and in particular, ranging from 2.8 to 6.

The polydispersity index I of the polymer is equal to the ratio of the average mass Mw to the average mass Mn.

the average molecular weights are determined by weight (Mw) and number (Mn) by liquid chromatography by gel permeation chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).

The weight-average mass (Mw) of the block polymer is preferably less than or equal to 300 000, it is for example from 35 000 to 200 000 and better still from 45 000 to 150 000.

The number-average mass (Mn) of the block polymer is preferably less than or equal to 70 000, it is for example from 10 000 to 60 000 and better still from 12 000 to 50 000.

Each sequence or block of the block polymer is derived from one type of monomer or from several different types of monomer.

This means that each block may consist of a homopolymer or a copolymer; this copolymer constituting the block may be his turn random or alternating.

The glass transition temperatures indicated for the first and second blocks may be theoretical Tg values ​​determined from the theoretical Tg values ​​of the constituent monomers of each of the sequences, which can be found in a reference manual such as the Polymer Handbook, 3 ^ ed 1989 ,. John Wiley, according to the following relationship, known as Fox's law:

1 / Tg = Σ (tσι / Tg,), tr i-j being the mass fraction of the monomer i in the sequence considered and * Tg being the glass transition temperature of the homopolymer of the monomer i. Unless otherwise indicated, the Tg values ​​indicated for the first and second blocks in the present patent application are theoretical Tg.

The difference between the glass transition temperatures of the first and second blocks is generally greater than 10 ° C, preferably greater than 20 ° C and better still greater than 30 ° C.

In particular, the block polymer comprises at least one first block and at least one second sequence such that the first block may be chosen from: - a) a sequence having greater than or equal to Tg 40 ° C, b) a sequence having a Tg less than or equal to 20 ° C, c) a block with a Tg of between 20 and 40 ° C, and the second sequence can be chosen from a category a), b) or c) different from the first sequence.

Is meant in the, present invention, by the expression:

"Between ... and ...", a range of values ​​which the terminals mentioned are excluded, and

"... To ..." and "from ... to ...", a range of values ​​whose terminals are included.

a) Block with a Tg of greater than or equal to 40 ° C

The block with a Tg of greater than or equal to 40 ° C for example a Tg ranging from 40 to 150 ° C, preferably greater than or equal to 50 ° C, for example ranging from 50 ° C to 120 ° C and better still greater or equal to 60 ° C, for example ranging from 60 ° C to 120 ° C.

The block with a Tg greater than or equal to 40 ° C may be a homopolymer or a copolymer.

The block with a Tg of greater than or equal to 40 ° C may be totally or partially derived from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature exceeding 40 ° C.

In the case where this block is a homopolymer, it is derived from monomers which are such (s) that the homopolymers prepared from these monomers have glass transition temperatures greater than or equal to 40 ° C. this first sequence may be a homopolymer consisting of one type of monomer (for which the Tg of the corresponding homopolymer is greater than or equal to 40 ° C).

In the case where the first block is a copolymer, it may be totally or partially derived from one or more monomers, the nature and concentration are chosen such that the Tg of the resulting copolymer is greater than or equal to 40 ° C. The copolymer may for example include:

- Monomers which are such (s) that the homopolymers prepared from these monomers have or above Tg 40 ° C, for example a Tg ranging from 40 to 150 ° C, preferably greater than or equal to 50 ° C , for example ranging from 50 ° C to 120 ° C and better still greater than or equal to 60 ° C, for example ranging from 60 ° C to 120 ° C, and

- Monomers which are such (s) that the homopolymers prepared from these monomers have lower Tg at 40 ° C, chosen from monomers with a Tg of between 20 to 40 ° C and / or monomers with a Tg of less than or equal to 20 ° C, for example a Tg ranging from -100 to 20 ° C, preferably below 15 ° C, especially ranging from - 80 ° C to 15 ° C and better less than 10 ° C, for example ranging from -50 ° C to 0 ° C, as described further.

The monomers whose homopolymers have a temperature higher glass transition or equal to 40 ° C are preferably chosen from the following monomers, also known as the main monomers:

- Methacrylates of formula CH₂ = C (CH₃) COOR₁ wherein R represents an unsubstituted alkyl group, linear or branched, containing from 1 to 4 carbon atoms, such as methyl, ethyl, propyl or isobutyl group or R represents a cycloalkyl group C₄ -C |₂

- CH formula acrylates₂ = CH-COOR₂ wherein R₂ is cycloalkyl C₄ to |₂ such as isobornyl acrylate or a tert-butyl group,

- (Meth) acrylamides of formula:

<img id="imgf000011_0001" he="19" wi="57" file="imgf000011_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein R₇ and R₈ identical or different, each represent a hydrogen atom or an alkyl group -C₁₂ linear or branched, such as n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl; or R₇ is H and R₈ represents a 1, 1-dimethyl-3-oxobutyl group, and R 'denotes H or methyl. Examples of monomers that may be mentioned include N-butylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N, N-dibutylacrylamide,

- And mixtures thereof.

Particularly preferred main monomers are methyl methacrylate, (meth) acrylate, isobutyl (meth) isobornyl acrylate and mixtures thereof.

b) Block with a Tg less than or equal to 20 ° C.

The block with a Tg less than or equal to 20 ° C for example a Tg ranging from - 100-20 ° C, preferably less than or equal to 15 ° C, especially ranging from -80 ° C to 15 ° C and preferably less or equal to 10 ° C, for example ranging from -50 ° C to 0 ° C.

The block with a Tg less than or equal to 20 ° C may be a homopolymer or a copolymer.

The block with a Tg less than or equal to 20 ° C may be totally or partially derived from one or more monomers which are such (s) that the homopolymer prepared from these monomers has a glass transition temperature or equal to 20 ° C.

In the case where this block is a homopolymer, it is derived from monomers which are such (s) that the homopolymers prepared from these monomers have glass transition temperatures less than or equal to 20 ° C. This second block may be a homopolymer consisting of one type of monomer (for which the Tg of the corresponding homopolymer is less than or equal to 20 ° C).

In the case where the block with a lower or Tg at 20 ° C is a copolymer, it may be totally or partially derived from one or more monomers, the nature and concentration are chosen such that the Tg of the resulting copolymer is less than or equal to 20 ° C. It may for example comprise - One or more monomers whose corresponding homopolymer has a Tg of less than or equal to 20 ° C, for example a Tg ranging from -100 ° C to 20 ° C, preferably below 15 ° C, especially ranging from - 80 ° C to 15 ° C and preferably below 10 ° C, for example ranging from -50 ° C to 0 ° C and - one or more monomers whose corresponding homopolymer has a Tg greater than 20 ° C, such as monomers with a Tg of greater than or equal to 40 ° C, for example a Tg ranging from 40 to 150 ° C, preferably greater than or equal to 50 ° C, for example ranging from 50 ° C to 120 ° C and better still greater than or equal to 60 ° C, for example ranging from 60 ° C to 120 ° C and / or monomers with a Tg of between 20 and 40 ° C, as described above.

Preferably, the block with a Tg less than or equal to 20 ° C is a homopolymer.

The monomers whose homopolymer has a Tg of less than or equal to 20 ° C are preferably chosen from the following monomers, or main monomer:

- CH formula acrylates₂ = CHCOOR₃,

R₃ representing a substituted alkyl group at C_12ι linear or branched, with the exception of the tert-butyl group, in which is (are) optionally intercalated (s) one or more heteroatoms selected from O, N, S,

- Methacrylates of formula CH₂ = C (CH₃) COOR₄,

R₄ representing a substituted alkyl C₆ -C₁₂ linear or branched, in which is (are) optionally intercalated (s) one or more heteroatoms selected from 0, N and S;

- A formula of vinyl esters₅-CO-O-CH = CH₂ wherein R₅ is alkyl C₄ -C₁₂ straight or branched;

- Vinyl ethers of C₄ -C₁₂,

- N-alkyl C -C₁₂ acrylamides, such as N-octylacryiamide,

- And mixtures thereof. Particularly preferred main monomers for the block with a Tg less than or equal to 20 ° C are alkyl acrylates whose alkyl chain contains from 1 to 10 carbon atoms, except the tert-butyl group, such as acrylate methyl acrylate, isobutyl acrylate, 2-ethylhexyl and mixtures thereof.

c) Block with a Tg of between 20 and 40 ° C.

The sequence which has a Tg of between 20 and 40 ° C may be a homopolymer or a copolymer.

10

The block with a Tg of between 20 and 40 ° C may be totally or partially derived from one or more monomers which are such (s) that the homopolymer prepared from these monomers has a glass transition temperature between 20 and 40 ° C.

^'15

The block with a Tg of between 20 and 40 ° C may be totally or partly from monomers which are such (s) that the corresponding homopolymer has a Tg of greater than or equal to 40 ° C and from monomers which are such ( s) that the corresponding homopolymer has a Tg less than or equal to 20 ° C.

20

In the case where this block is a homopolymer, it is derived from monomers (or main monomer) which are such (s) that the homopolymers prepared from these monomers have glass transition temperatures between 20 and 40 ° C. This first block may be a homopolymer consisting of a single type of monomer 25 (for which the Tg of the corresponding homopolymer ranges from 20 ° C to 40 ° C).

The monomers whose homopolymer has a glass transition temperature between 20 and 40 ° C are preferably chosen from methacrylate, n-butyl acrylate, cyclodecyl acrylate, neopentyl isodecylacrylamide and mixtures thereof.

thirty

In the case where the block with a Tg of between 20 and 40 ° C is a copolymer, it is totally or partially derived from one or more monomers (or main monomer) whose nature and concentration are chosen such that the Tg of the resulting copolymer is between 20 and 40 ° C.

35 Advantageously, the block with a Tg of between 20 and 40 ° C is a copolymer outcome in whole or in part: - Main monomers whose corresponding homopolymer has a Tg of greater than or equal to 40 ° C, for example a Tg ranging from 40 ° C to 150 ° C, preferably greater than or equal to 50 ° C, for example ranging from 50 to 120 ° C and better still greater than or equal to 60 ° C, for example ranging from 60 ° C to 120 ° C, as described above, and / or - the main monomers whose corresponding homopolymer has a Tg of less than or equal at 20 ° C, for example a Tg ranging from -100 to 20 ° C, preferably less than or equal to 15 ° C, especially ranging from -80 ° C to 15 ° C and better still less than or equal to 10 ° C, example ranging from -50 ° C to 0 ° C, as described above, the said monomers being chosen such that the Tg of the copolymer forming the first block is between 20 and 40 ° C.

Such main monomers are chosen, for example methyl methacrylate, and isobornyl methacrylate, butyl acrylate, acrylate, 2-ethylhexyl and mixtures thereof.

Preferably, the proportion of the second block with a Tg less than or equal to 20 ° C is from 10 to 85% by weight of the polymer, more preferably from 20 to 70% and more preferably 20 to 50%.

Preferably, each of the first and second blocks comprises at least one monomer selected from acrylic acid, acrylic acid esters, (meth) acrylic acid, esters of (meth) acrylic acid and mixtures thereof.

Advantageously, each of the first and second blocks is totally derived from at least one monomer selected from acrylic acid, acrylic acid esters, (meth) acrylic acid, esters of (meth) acrylic acid and mixtures thereof.

Each of the blocks may contain in small proportion at least one constituent monomer of the other sequence. Thus, the first block may contain at least one constituent monomer of the second block, and vice versa.

Each of the first and / or second blocks (Fri) comprise, in addition to the monomers indicated above, one or more other monomers known as additional monomers, different from the main monomers mentioned above. The nature and amount of this or these additional monomer are chosen so that the sequence in which they are present has the desired glass transition temperature.

This additional monomer is for example selected from: a) hydrophilic monomers such as:

- Unsaturated monomers (s) ethylenic (s) comprising at least one carboxylic or sulfonic acid function, for instance: acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, vinylphosphoric acid and the salts thereof,

- Unsaturated monomers (s) ethylenic (s) comprising at least one tertiary amine function, for instance 2-vinylpyrjdine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylamide and dimethylaminopropylmethacrylamide, and salts thereof ,

- Methacrylates of formula CH₂ = C (CH₃) COOR₆ wherein R₆ represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as methyl, ethyl, propyl or isobutyl group, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups (such as methacrylate 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I, F), such as trifluoroethyl methacrylate,

- Methacrylates of formula CH₂ = C (CH₃) COOR₉,

R₉ Representative alkyl C₆ -C₁₂ linear or branched, in which is (are) optionally intercalated (s) one or more heteroatoms selected from 0, N and S, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups and halogen atoms ( Cl, Br, I, F);

- CH formula acrylates₂ = CHCOOR₁₀,

R₁₀ is alkyl to C₁₂ linear or branched substituted by one or more substituents chosen from hydroxyl groups and halogen atoms (Cl, Br, I and F), such as acrylate, 2-hydroxypropyl acrylate and 2-hydroxyethyl, or R₁₀ represents an alkyl (CC₁₂) O-POE (polyoxyethylene) with repetition of the oxyethylene unit 5 to 30 times, for example methoxy-POE, or R₁₀represents a polyoxyethylene group comprising from 5 to 30 ethylene oxide units

b) ethylenically unsaturated monomers comprising one or more silicon atoms, such as methacryloxypropyltrimethoxysilane trimethoxy silane, methacryloxypropyl tris (trimethylsiloxy) silane, - And mixtures thereof.

Particularly preferred additional monomers are acrylic acid, acid, methacrylic acid, trifluoroethyl methacrylate and mixtures thereof.

According to one embodiment, each first and second block of the block polymer comprises at least one monomer selected from esters of (meth) acrylic acid and optionally at least one additional monomer such as (meth) acrylic acid, and mixtures thereof.

According to another embodiment, each first and second block of the block polymer is totally derived from at least one monomer selected from esters of (meth) acrylic acid and optionally at least one additional monomer such as the (meth) acrylic acid, and mixtures thereof.

According to a preferred embodiment, the block polymer is a non-silicone polymer, i.e. a polymer free of silicon atoms.

This or these additional monomers represent (s) generally a less than or equal to 30% by weight, for example from 1 to 30% by weight, preferably 5 to 20% by weight and, more preferably, from 7 to 15 % by weight of the total weight of the first and / or second blocks.

The block polymer may be obtained by radical solution polymerization according to the following preparation process: a portion of the polymerization solvent is introduced into a suitable reactor and heated until the adequate temperature for the polymerization (typically between 60 and 120 ° C. ), once this temperature is reached, the constituent monomers of the first block are introduced in the presence of a portion of the polymerization initiator, after a time T corresponding to a maximum conversion of 90%, the monomers constituting the second block and the rest of the initiator are introduced, - is allowed to react for a time T '(ranging from 3 to 6 hours) after which the mixture is cooled to room temperature, there was obtained polymer dissolved in the polymerization solvent. First Embodiment

According to a first embodiment, the block polymer comprises a first block having an equal or higher Tg to 40 ° C, as described above in a) and a second block with a Tg of less than or equal to 20 ° C as described above in b).

Preferably, the first block with a Tg of greater than or equal to 40 ° C is a copolymer derived from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature exceeding 40 ° C, such as the monomers described above. Advantageously, the second block with a Tg of less than or equal to 20 ° C is a homopolymer derived from monomers which are such (s) that the homopolymer prepared from these monomers has a glass transition temperature not exceeding 20 ° C. such as the monomers described above.

Preferably, the proportion of the block with a Tg greater than or equal to 40 ° C is from 20 to 90% by weight of polymer, preferably from 30 to 80% and more preferably 50 to 70%.

Preferably, the proportion of the block with a Tg less than or equal to 20 ° C is from 5 to 75% by weight of polymer, preferably from 15 to 50% and better still from 25 to 45%.

Thus, in a first variant, the polymer according to the invention may comprise: - a first Tg of greater than or equal to 40 ° C, for example having a Tg ranging from 70 to 110 ° C, which is a methyl methacrylate copolymer / acrylic acid,

- A second sequence Tg of less than or equal to 20 ° C, for example ranging from 0 to 20 ° C, which is a methyl acrylate homopolymer, and

- An intermediate block which is a methyl methacrylate / acrylic acid / methyl acrylate.

In a second variant, the polymer according to the invention may comprise:

- A first sequence of Tg greater than or equal to 40 ° C, for example ranging from 70 to 100 ° C, which is a copolymer of methyl methacrylate / acrylic acid / trifluoroethyl methacrylate,

- A second sequence Tg of less than or equal to 20 ° C, for example ranging from 0 to 20 ° C, which is a methyl acrylate homopolymer, and an intermediate block which is a random copolymer of me ethyl methacrylate / acrylic acid / methyl acrylate / trifluoroethyl methacrylate.

In a third variant, the polymer according to the invention may comprise: - a first Tg of greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is an isobornyl acrylate / methacrylate isobutyl,

- A second sequence Tg of less than or equal to 20 ° C, for example ranging from -85 to - 55 ° C, which is a homopolymer of acrylate 2-ethylhexyl and

- An intermediate block which is an isobornyl acrylate random copolymer / isobutyl methacrylate / acrylate, 2-ethylhexyl.

In a fourth variant, the polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is an isobornyl acrylate / methyl methacrylate, - a second sequence Tg of less than or equal to 20 ° C , for example ranging from -85 to -55 ° C, which is a homopolymer of 2-ethyl hexyl acrylate and

- An intermediate block which is an isobornyl acrylate random copolymer / methyl methacrylate / acrylate, 2-ethylhexyl.

According to a fifth variant, the polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example ranging from 95 to 125 ° C, which is an isobornyl acrylate / isobornyl methacrylate;

- A second sequence Tg of less than or equal to 20 ° C, for example ranging from -85 to -55 ° C, which is a homopolymer of 2-ethylhexyl acrylate, and - an intermediate block which is an acrylate random copolymer isobornyl acrylate / isobornyl methacrylate / acrylate, 2-ethylhexyl.

According to a sixth variant, the polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is a copolymer of isobornyl methacrylate / isobutyl methacrylate,

- A second sequence Tg of less than or equal to 20 ° C, for example ranging from -35 to -5 ° C, which is an isobutyl acrylate homopolymer and

- An intermediate block which is a random copolymer of isobornyl methacrylate / isobutyl methacrylate / isobutyl acrylate.

According to a seventh variant, the polymer according to the invention may comprise: - A first Tg of greater than or equal to 40 ° C, for example ranging from 95 to 125 ° C, which is an isobornyl acrylate / isobornyl methacrylate,

- A second sequence of less than or equal to Tg 20 ° C, for example ranging from -35 to -5 ° C, which is a homopolymer of isobutyl acrylate and - an intermediate block which is an isobornyl acrylate random copolymer / isobornyl methacrylate / isobutyl acrylate.

According to an eighth variant, the polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example ranging from 60 to 90 ° C, which is an isobornyl acrylate / isobutyl methacrylate,

- A second sequence Tg of less than or equal to 20 ° C, for example ranging from -35 to -5 ° C, which is an isobutyl acrylate homopolymer and

- An intermediate block which is an isobornyl acrylate random copolymer / isobutyl methacrylate / isobutyl acrylate.

The following examples illustrate without limitation polymers corresponding to this first embodiment. The amounts are expressed in grams.

Example 1 Preparation of a polymer Poly (isobornyl acrylate / methyl methacrylate / acrylate, 2-ethylhexyl

100 g of isododecane are introduced into a 1 liter reactor and the temperature is increased so as to pass from room temperature (25 ° C) to 90 ° C over 1 hour.

are then added at 90 ° C and in 1 hour, 150 g of isobornyl acrylate, 60 g of methyl methacrylate, 110 g of isododecane and 1, 8 g of 2.5- Bis (2- ethylhexanoylperoxy) -2.5 -diméthylhexane (Trigonox^® 141 Akzo Nobel).

The mixture was held for 1 h 30 to 90 ° C. Is then introduced into the above mixture, still at 90 ° C in 30 minutes, 90 g of acrylate 2-ethylhexyl, 90 g of isododecane and 1, 2 g of 2.5- Bis (2- ethylhexanoylperoxy) -2.5 -diméthylhexane.

The mixture is kept 3 hours at 90 ° C and then the whole is cooled.

This gave a solution containing 50% polymer active material in isododecane.

A polymer comprising a first sequence or block poly (isobornyl acrylate / methyl methacrylate) having a Tg of 100 ° C, a second sequence polyacrylate, 2-ethylhexyl with a Tg of - 70 ° C and an intermediate block which is an isobornyl acrylate random polymer / methyl methacrylate / 2 ethyl hexyl acrylate.

This polymer has a weight-average mass of 76 500 and an average weight of 22 000, ie a polydispersity index I of 3.48.

Example 2 Preparation of a polymer Poly (isobornyl acrylate / isobornyl methacrylate / acrylate 2-ethylhexyl)

100 g of isododecane are introduced into a 1 liter reactor and the temperature is increased so as to pass from room temperature (25 ° C) to 90 ° C over 1 hour. are then added at 90 ° C and in 1 hour, 105 g of isobornyl acrylate, 105 g of isobornyl methacrylate, 110 g of isododecane and 1, 8 g of 2.5- Bis (2-ethy! hexanoylperoxy ) -2.5-dimethyl hexane (Trigonox^® 141 Akzo Nobel). The mixture was held for 1 h 30 to 90 ° C.

Is then introduced into the above mixture, still at 90 ° C in 30 minutes, 90 g of acrylate 2-ethylhexyl, 90 g of isododecane and 1, 2 g of 2.5- Bis (2- ethylhexanoylperoxy) -2.5 -diméthylhexane. The mixture is kept 3 hours at 90 ° C and then the whole is cooled.

This gave a solution containing 50% polymer active material in isododecane.

A polymer comprising a first sequence or block poly (isobornyl acrylate / isobornyl methacrylate) having a Tg of 110 ° C, a second polyacrylate sequence of 2-ethylhexyl acrylate having a Tg of - 70 ° C and a intermediate block which is an acrylate random polymer isobornyl acrylate / isobornyl methacrylate / acrylate, 2-ethylhexyl.

This polymer has a weight-average mass of 103 900 and an average weight of 21 300, ie a polydispersity index I of 4.89.

Example 3 Preparation of a polymer of Poly (isobornyl acrylate / isobutyl methacrylate / isobutyl acrylate)

100 g of isododecane are introduced into a 1 liter reactor and the temperature is increased so as to pass from room temperature (25 ° C) to 90 ° C over 1 hour. are then added at 90 ° C and in 1 hour, 120 g of isobornyl acrylate, 90 g of isobutyl methacrylate, 110 g of isododecane and 1, 8 g of 2.5- Bis (2- ethylhexanoylperoxy) -2.5 -diméthylhexane (Trigonox^® 141 Akzo Nobel).

The mixture was held for 1 h 30 to 90 ° C.

then introduced into the above mixture, still at 90 ° C in 30 minutes, 90 g of isobutyl acrylate, 90 g of isododecane and 1, 2 g of 2.5- Bis (2-ethylhexanoylperoxy) -2.5- dimethylhexane.

The mixture is kept 3 hours at 90 ° C and then the whole is cooled.

This gave a solution containing 50% polymer active material in isododecane.

A polymer comprising a first sequence or block poly (isobornyl acrylate / isobutyl methacrylate) having a Tg of 75 ° C, a second sequence of isobutyl acrylate having a Tg of - 20 ° C and an intermediate block which is an acrylate random polymer isobornyl acrylate / isobutyl methacrylate / isobutyl acrylate.

This polymer has a weight-average mass of 144 200 and an average weight of 49 300, ie a polydispersity index I of 2.93.

Second Embodiment

According to a second embodiment, the block polymer comprises a first block having a glass transition temperature (Tg) of between 20 and 40 ° C, according to the blocks described in c) and a second block having a glass transition temperature or equal to 20 ° C, as described above in b) or a glass transition temperature exceeding 40 ° C, as described in a) above.

Preferably, the proportion of the first block with a Tg of between 20 and 40 ° C is from 10 to 85% by weight of polymer, preferably from 30 to 80% and even better still from 50 to 70%.

When the second sequence is a sequence having greater than or equal to Tg 40 ° C, it is preferably present in a proportion ranging from 10 to 85% by weight of polymer, preferably from 20 to 70% and better still from 30 to 70 %. When the second sequence is a sequence having less than or equal to Tg 20 ° C, it is preferably present in a proportion ranging from 10 to 85% by weight of polymer, preferably from 20 to 70% and better still from 20 to 50 %.

Preferably, the first block with a Tg of between 20 and 40 ° C is a copolymer derived from monomers which are such (s) that the corresponding homopolymer has a Tg of greater than or equal to 40 ° C and from monomers which are such ( s) that the corresponding homopolymer has a Tg less than or equal to 20 ° C.

Advantageously, the second block with a Tg less than or equal to 20 ° C or having a Tg greater than or equal to 40 ° C is a homopolymer.

Thus, according to first variant of this second embodiment, the block polymer may comprise:

- A first Tg sequence comprised between 20 and 40 ° C, for example having a Tg from 25 to 39 ° C, which is a copolymer comprising at least one methyl acrylate monomer, at least one monomer of methyl methacrylate and at least one acrylic acid monomer,

- A second Tg of greater than or equal to 40 ° C, for example ranging from 85 to 125 ° C, which is a homopolymer composed of methyl methacrylate monomers, and - an intermediate block comprising at least one methyl acrylate monomer, methacrylate methyl and

- An intermediate block comprising methyl methacrylate, at least one acrylic acid monomer and at least one methyl acrylate monomer.

According to a second variant of this second embodiment, the block polymer may comprise:

- A first sequence Tg of between 20 and 40 ° C, for example with a Tg from 21 to 39 ° C, which is a copolymer comprising isobornyl acrylate / isobutyl methacrylate / acrylate, 2-ethylhexyl, - a second sequence Tg of less than or equal to 20 ° C, for example ranging from -65 to - 35 ° C, which is a methyl methacrylate homopolymer and

- An intermediate block which is an isobornyl acrylate random copolymer / isobutyl methacrylate / acrylate, 2-ethylhexyl.

In a third variant of this second embodiment, the block polymer may comprise: - A first sequence Tg of between 20 and 40 ° C, for example with a Tg from 21 to 39 ° C, which is an isobornyl acrylate / methyl acrylate / acrylic acid,

- A second Tg of greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is an acrylate homopolymer of isobornyl

- An intermediate block which is an isobornyl acrylate random copolymer / methyl acrylate / acrylic acid.

The composition according to the invention preferably contains from 0.1 to 60% by weight of active material (or dry weight) of the polymer, preferably from 0.5 to 50% by weight, and more preferably from 1 to 40% in weight.

film-forming agent The composition of the invention also contains at least one film forming agent which may be an organic or inorganic polymer. The film former, when an organic polymer is not a polymer film-forming ethylenic linear block as described above.

In one embodiment, the film-forming organic polymer is at least one polymer selected from the group comprising: film-forming polymers soluble in the organic liquid medium, in particular fat-soluble polymers, when the organic liquid medium comprises at least one oil, - the dispersible film-forming polymers in the organic solvent medium, in particular polymers in the form of non-aqueous dispersions of polymer particles, preferably dispersions in silicone oils or hydrocarbon; in one embodiment, non-aqueous polymer dispersions comprise polymer particles stabilized on their surface by at least one stabilizing agent; these non-aqueous dispersions are often called "NAD [non-aqueous dispersions]", aqueous dispersions of film-forming polymer particles, often called "latex"; in this case, the composition should, besides the organic liquid medium, an aqueous phase, - the water-soluble film-forming polymers; in this case, the composition should, besides the organic liquid medium, an aqueous phase. In one embodiment, the film former is a water soluble film-forming organic polymer in the organic liquid medium.

1 / soluble polymers the organic liquid medium When the organic liquid medium of the composition comprises at least one oil, the film forming agent may be a polymer soluble in said oil. In this case, it is called soluble polymer. The soluble polymer may be of any chemical type and may especially be chosen from:

a) homopolymers and liposoluble copolymers and amorphous olefins, cycloolefins, of butadiene, isoprene, styrene, ethers, vinyl esters or amides, esters or amides of (meth) acrylic polymer containing a alkyl group C ^ o straight, branched or cyclic, and preferably amorphous. Preferred homopolymers and fat-soluble copolymers are obtained from monomers selected from the group consisting of (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth ) acrylate, lauryl (meth) acrylate, isopentyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylate, tert-butyl (meth) acrylate, tridecyl (meth) acrylate, or mixtures thereof. May be mentioned, for example, the copolymer of alkyl acrylate / cycloalkyl acrylate copolymer sold by PHOENIX CHEM. GIOVAREZ under the name AC-5099 ML, and vinylpyrrolidone copolymers such as copolymers of an alkene C₂ -C_thirtySuch as C₃ -C₂₂And combinations thereof, may be used. As examples of VP copolymers which can be used in the invention include the copolymers of VP / vinyl laurate, VP / vinyl stearate, polyvinylpyrrolidone (PVP) butylated VP / hexadecene, VP / triacontene or VP / acrylic acid / lauryl methacrylate. As specific copolymers liposoluble include: i) graft silicone-acrylic polymers having a silicone backbone, acrylic grafts or having an acrylic skeleton and silicone grafts such as the product sold under the name SA 70.5 by 3M and described in US patents 5,725,882, US 5,209,924, US 4,972,037, US 4,981,903, US 4,981,902, US 5,468,477, and in U.S. Patent 5,219,560 and EP 0,388,582.

ii) the fat-soluble polymers bearing fluorinated groups belonging to one of the classes described in the text above, in particular those described in US Patent 5,948,393, copolymers of (meth) acrylate has! Kyle / ( meth) acrylate, perfluoroalkyl described in patents EP 0815836 and US 5,849,318. iii) polymers or copolymers resulting from the polymerization or copolymerization of an ethylenic monomer comprising one or more ethylenic bonds, preferably conjugated (or dienes). As polymers or copolymers resulting from the polymerization or copolymerization of an ethylenic monomer, there may be used vinyl copolymers, acrylic or methacrylic.

In one embodiment, the film former is a block copolymer comprising at least one block composed of styrene units or styrene derivatives (e.g., methylstyrene, chlorostyrene or chloromethylstyrene). The copolymer comprising at least one styrene block may be a diblock or triblock copolymer or a multiblock copolymer, star or radial. The copolymer comprising at least one styrene block may further comprise, for example, an alkyl styrene block (AS), an ethylene unit / butylene (EB) an ethylene unit / propylene (EP), a butadiene block (B), isoprene block (I), acrylate block (a), a methacrylate block (MA) or a combination of these blocks. The copolymer comprising at least one block composed of styrene units or styrene derivatives may be a triblock copolymer and in particular of the polystyrene / polyisoprene or polystyrene / polybutadiene type such as those sold or manufactured under the name "Luvitol HSB" by BASF and those of the type polystyrene / copoly (ethylene-propylene) or alternatively of the polystyrene / copoly (ethylene / butylene), such as those sold or manufactured under the trademark "Kraton" by Shell Chemical Co. or Gelled Permethyl 99A by Penreco, may be used. Styrene-methacrylate copolymers may also be used. copolymer comprising at least one block composed of styrene units or styrene derivatives may be, for example, Kraton G1650 (SEBS), Kraton G1651 (SEBS), Kraton G1652 (SEBS), Kraton G1657X (SEBS), Kraton G1701X (MS), Kraton G1702X (MS), Kraton G1726X (SEB), the Kraton D-1101 (SBS), the Kraton D-1102 (SBS), the Kraton D-1107 (SIS), Gelled Permethyl 99A -750, the Gelled Permethyl 99A-753-58 (mixture of star block polymer and triblock polymer), the Gelled Permethyl 99A-753-59 (mixture of star block polymer and triblock polymer), and the 5970 Versagel Versagel 5960 from Penreco (mixture of star polymer and triblock polymer in isododecane), and OS 129880, OS 129881 and OS 84383 from Lubrizol in (styrene-methacrylate).

In one embodiment, the film forming agent is selected from copolymers of vinyl ester (the vinyl group being directly linked to the oxygen atom ester group and the vinyl ester containing a saturated hydrocarbon radical, linear or branched, of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and of at least one other monomer which may be a vinyl ester (other than the 'already present vinyl ester), an α-olefin (having from 8 to 28 carbon atoms), an alkyl vinyl ether (the alkyl group comprises from 2 to 18 carbon atoms) or an allyl or methallyl ester (having a hydrocarbon radical saturated linear or branched, of 1 to 19 carbon atoms, linked to the ester carbonyl). These copolymers may be partially crosslinked using crosslinking agents which can be either of the vinyl type or of the allyl or methallyl type, such as tetraailyloxyethane, divinylbenzene, divinyl octanedioate, divinyl octadecanedioate divinyl.

Examples of such copolymers include the following copolymers: vinyl acetate / allyl stearate, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecyl , vinyl propionate / allyl laurate, vinyl propionate / vinyl laurate, vinyl stearate / 1-octadecene, vinyl acetate / 1-dodecene, vinyl stearate / ethyl vinyl ether, vinyl propionate / cetyl vinyl ether, stearate vinyl / allyl acetate, dimethyl-2, 2 octanoate vinyl / vinyl laurate, dimethyl-2, 2 pentanoate allyl / vinyl laurate, vinyl dimethylpropionate / vinyl stearate, allyl dimethyl propionate / stearate vinyl ether, vinyl propionate / vinyl stearate, crosslinked with 0.2% divinylbenzene, vinyl dimethylpropionate / vinyl laurate, crosslinked with 0.2% divinylbenzene, vinyl acetate / octadecyl vinyl ether, crosslinked with 0.2% tetraailyloxyethane, vinyl acetate / allyl stearate, crosslinked with 0.2% divinylbenzene, vinyl acetate / 1-octadecene, crosslinked with 0.2% divinylbenzene, and allyl propionate / stearate allyl crosslinked with 0.2% divinylbenzene. As liposoluble film-forming polymers, liposoluble copolymers may also be made, and especially those resulting from copolymerization of vinyl esters containing from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, and alkyl radicals having from 10 to 20 carbon atoms.

Such liposoluble copolymers may be chosen from polyvinyl stearate copolymers, polyvinyl stearate crosslinked with divinylbenzene, with diallyl ether or with diallyl phthalate, polystearyl (meth) acrylate, vinyl laurate , poly (meth) acrylate, these poly (meth) acrylates to be crosslinked with ethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate. The fat-soluble copolymers defined above are known and described in the application FR-A-2232303; they may have an average molecular weight ranging from 2,000 to 500,000, preferably 4,000 to 200,000. As examples of liposoluble polymers which can be used in the invention include polyalkylenes, alkene copolymers of C₂-C₂o, particularly polybutene.

b) amorphous and fat-soluble polycondensates, preferably not comprising donor groups hydrogen interactions, in particular aliphatic polyesters having alkyl side chains Oμso or polyesters resulting from the condensation of fatty acid dimers, or even polyesters comprising a silicone segment in the form of a sequence, graft or terminal group, solid at room temperature as defined in the patent application FR 0,113,920, not yet published.

c) amorphous and fat-soluble polysaccharides comprising alkyl side chains (ether or ester), in particular alkyl celluloses having an alkyl radical C ^ -C₈ saturated or unsaturated, linear or branched, such as ethylcellulose and propylcellulose.

The film forming polymer may be chosen in particular from cellulose polymers such as nitrocellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, ethyl cellulose, or alternatively polyurethanes, acrylic polymers, vinyl polymers, polyvinyl butyrals, alkyd resins, resins derived from aldehyde condensation products, such as arylsulfonamide-formaldehyde resins, for instance toluene sulfonamide formaldehyde resin, epoxy resins aryl sulfonamide.

Film-forming polymers that may especially use the RS 1/8 sec nitrocellulose; RS VA sec. ;^ΛΛ sec. ; RS 5 sec. ; RS 15 sec. ; RS 35 sec. ; RS 75 sec; RS 150 sec; AS VA sec. ; AS 34 sec. ; SS% dry. ; SS¹/ Έ sec. ; SS 5 sec, in particular sold by the company Hercules; toluene sulfonamide formaldehyde resin "Ketjentflex MS80" from Akzo or "Santolite MHP", "Santolite MS 80" from the company Faconnier or "Resimpol 80" of the company PAN AMERICANA, the alkyd resin "Beckosol ODE 230-70-E "from the company Dainippon, acrylic resin" ACRYLOID B66 "from the company Rohm &amp; Haas, the polyurethane resin" Trixene PR 4127 "from the company Baxenden.

d) silicone resins soluble or swellable in silicone oils. These resins are partially crosslinked polyorganosiloxanes which, depending on the crosslinking taux- will be soluble or swellable by the silicone oils of the middle of the oil phase organic liquid. These silicone resins are selected from the following non-exhaustive list: MQ resins or trimethylsiloxysilicates polysilesquioxane or Crosslinked dimethicone / vinyldimethicone.

/// Non-aqueous dispersions of polymer particles

The composition may contain a film selected from non-aqueous dispersions of polymer particles agent. The particles are generally spherical. Prior to incorporation in the composition of the invention, the particles are generally dispersed in a physiologically acceptable liquid fatty phase, such as hydrocarbon-based oils or silicone oils. According to one embodiment, these dispersions are generally known as "NAD" (non aqueous dispersions) of polymer, as opposed to networks, which are aqueous polymer dispersions. These dispersions may especially be in the form of a stable dispersion of polymer nanoparticles in said fatty phase. In one embodiment, the nanoparticles have a size of between 5 nm and 600 nm. However, it is possible to obtain polymer particles of a size up to 1 micron.

One advantage of the polymer dispersion of the composition of the invention is the possibility of varying the glass transition temperature (Tg) of the polymer or polymer system (polymer plus additive of the plasticizer type), and therefore to pass a hard polymer to a more or less soft polymer, making it possible to adjust mechanical properties of the composition, depending on the intended application and in particular according to the deposited film.

Dispersion polymers can be used in the composition of the invention preferably have a molecular weight ranging from about 2,000 to 10 million, and a Tg ranging from -100 ° C to 300 ° C, and more preferably from -50 ° C to 50 ° C, and preferably -10 ° C to 100 ° C.

It is possible to use film-forming polymers, preferably having a low Tg of less than or equal to the temperature of the skin and especially less than or equal to 40 ° C. This gives a dispersion, which can form a film when applied to a support.

Mention may be made from film-forming polymers homopolymers or acrylic copolymers or vinyl radical, preferably having a Tg of less than or equal to 40 ° C and especially from -10 ° C to 30 ° C., used alone or in admixture. By the term "free radical polymer" means a polymer obtained by polymerization of monomers containing unsaturation, in particular ethylenic unsaturation, each monomer being capable of homopolymerizing (unlike polycondensates). Radical polymers may especially be vinyl polymers or copolymers, especially acrylic polymers.

The vinyl polymers may result from the polymerization of ethylenically unsaturated monomers containing at least one acid group and / or esters of these acidic monomers and / or amides of these acids.

Monomers bearing an acidic group, there can be used unsaturated carboxylic acids, β-ethylenic, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid. (Meth) acrylic acid and crotonic acid are preferably used, more preferentially (meth) acrylic acid.

Acid esters monomers are chosen advantageously among the esters of (meth) acrylic acid (also known as (meth) acrylates), for example (meth) acrylates, especially alkyl CC₂o and preferably in Cι_C₆(Meth) acrylates of an aryl, in particular aryl C₆-C₁₀, And (meth) acrylates, in particular a hydroxy C₂-C₆. (Meth) acrylates may be mentioned include (meth) acrylate, ethyl, butyl, isobutyl, 2-ethylhexyl and lauryl. (Meth) acrylates may be mentioned include (meth) acrylate and (meth) acrylate, 2-hydroxypropyl. (Meth) aryl acrylates may be mentioned include acrylate benzyl or phenyl.

Esters of (meth) acrylic acid being particularly preferred are (meth) acrylates.

Radical polymers which are preferably used are the acid of (meth) acrylic acid and a (meth) acrylate including an alkyl DC₄. More preferably, one may use methyl acrylates, optionally copolymerized with acrylic acid. Amides of acidic monomers may be mentioned include (meth) acrylamides, and especially N-alkyl (meth) acrylamides, in particular a C₂-Cι₂, Such as N-ethyl acrylamide, Nt-butylacrylamide and N-octylacrylamide, N-dialkyI (CC₄) (Meth) acrylamides.

The vinyl film-forming polymers can result from the polymerization of ethylenically unsaturated monomers having at least one acid group and / or esters of these acidic monomers and / or amides of these acidic monomers.

An acid group bearing monomer, there can be used unsaturated carboxylic acids, α, β-ethylenic such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid. preferably acid is used (meth) acrylic acid and crotonic acid, and more préférentiellem'ent (meth) acrylic acid.

The acid monomer esters are advantageously chosen from esters of (meth) acrylic acid (also known as (meth) acrylates), especially (meth) acrylates, especially alkyl CC_thirty, Preferably DC₂₀, (Meth) acrylates, aryl, in particular aryl C₆-C ₀, (Meth) acrylates, in particular hydroxy-C₂-C₆ . From (meth) acrylates include methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl cyclohexyl methacrylate. From (meth) acrylates include hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, hydroxyethyl methacrylate, 2-hydroxypropyl.

Among the (meth) aryl acrylates that may be mentioned are benzyl acrylate and phenyl acrylate.

Esters of (meth) acrylic acid are particularly preferred are (meth) acrylates.

According to the present invention, the alkyl group of the esters may be either fluorinated or perfluorinated, that is to say that a portion or all of hydrogen atoms of the alkyl group are substituted by fluorine atoms.

As amides of acid monomers, there may be mentioned are (meth) acrylamides, and especially N-alkyl (meth) acrylamides, in particular alkyl C₂-C₁₂. Among the N- alkyl (meth) acrylamides include N-ethyl acrylamide, Nt-butyl acrylamide, N-t-octyl acrylamide and N-undecylacrylamide.

The vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers chosen from vinyl esters and styrene monomers. In particular, these monomers may be polymerized with acidic monomers and / or their esters and / or amides thereof, such as those mentioned above.

Examples of vinyl esters include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate. Styrene monomers include styrene and alpha-methyl styrene.

In a nonlimiting manner, the dispersion polymers of the invention may be chosen from polymers or the following copolymers: polyurethanes, polyurethane-acrylics, polyureas, polyurea-polyurethanes, polyester-polyurethanes, polyether-polyurethanes, polyesters, polyesteramides, fatty-chain polyesters, alkyds; polymers or acrylic copolymers and / or vinyl; acrylic-silicone copolymers; polyacrylamides; silicone polymers, for example silicones or polyurethanes acrylic silicones, and fluoropolymers, and mixtures thereof.

Or the polymer (s) in the oily dispersion may (can) represent (solids or active material) from 0.1% to 60% by weight of the composition, preferably from 2% to 40% and better still from 4% to 25%. For a stabilizer which is solid at room temperature, the amount of solids in the dispersion represents the total amount of polymer and stabilizer.

The liposoluble or dispersible polymers in the composition of the invention may also be used in an amount ranging from 0.01% to 20% (as active material) relative to the total weight of the composition, such as for example from 1% to 10%, if necessary.

III) Aqueous dispersions of polymer particles In another embodiment, the film-forming polymer may be chosen from aqueous dispersions of polymer particles, in the case where the composition according to the invention comprises an aqueous phase. The aqueous dispersion comprising one or more film-forming polymers may be prepared by those skilled in the art on the basis of his general knowledge, especially by emulsion polymerization or by dispersing the polymer previously formed.

Suitable film-forming polymers useful in the composition of the present invention include synthetic polymers of the polycondensate type or of radical type, the natural polymers and mixtures thereof.

Among the polycondensates, mention may also be anionic, cationic, nonionic and amphoteric surfactants, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea / polyurethanes, and mixtures thereof.

The polyurethanes may be for example an aliphatic polyurethane copolymer, cycloaliphatic or aromatic polyurea / polyurethane or polyurea comprising, alone or as a mixture: at least one linear polyester original sequence or branched aliphatic and / or cycloaliphatic and / or aromatic and / or at least one sequence of aliphatic polyether origin, and / or cycloaliphatic and / or aromatic and / or at least one silicone sequence, substituted or unsubstituted, branched or unbranched, for example polydimethylsiloxane or polymethylphenylsiloxane, and / or at least one sequence comprising fluorinated groups.

The polyurethanes as defined in the invention can also be obtained from branched or unbranched polyesters or from alkyds comprising mobile hydrogen which are modified by means of a polyaddition with a diisocyanate and a coreactive difunctional compound organic (for example dihydro, diamino or hydroxy-amino), further comprising either a carboxylic acid or carboxylate group or a sulfonate group or sulfonic acid or a neutralizable tertiary amine group or a quaternary ammonium group.

It can also be made of polyesters, polyesteramides, fatty-chain polyesters, polyamides and epoxy ester resins. The polyesters may be obtained in known manner by means of the polycondensation of aliphatic or aromatic diacids with aliphatic or aromatic diols or with polyols. Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid or sebacic acid may be used as aliphatic diacids. Terephthalic acid or isophthalic acid or a derivative such as phthalic anhydride, may be used as aromatic diacids. Ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol and 4,4-N- (1-methylpropylidene) bisphenol may be used as aliphatic diols. Glycerol, pentaerythritol, sorbitol and trimethylolpropane may be used as polyols.

Polyesteramides may be obtained in a similar manner to the polyesters, by polycondensation of diacids with diamines or aminoalcohols. Ethylenediamine, hexamethylenediamine and meta- or para-phenylenediamine may be used as diamine. Monoethanolamine can be used as amino alcohol.

As monomer bearing an anionic group which may be used during the polycondensation, mention may be made, for example, dimethylolpropionic acid, trimellitic acid or a derivative such as trimellitic anhydride, the sodium salt of 3- sulfopentanediol acid and the sodium salt of 5-sulpho-1,3-benzenedicarboxylic acid. Polyesters having a fatty chain can be obtained through the use of diols having a fatty chain during polycondensation. The epoxy ester resins may be obtained^' by polycondensation of fatty acids with a condensate at the ends of α, ω-diepoxy.

Radical polymers may in particular be polymers or acrylic copolymers and / or vinyl. Anionic radical polymers are preferred. As monomer bearing an anionic group which may be used during the radical polymerization, there may be mentioned acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid.

The acrylic polymers may result from the copolymerization of monomers selected from esters and / or amides of acrylic acid or methacrylic acid. Examples of monomers of the ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-éthylhexyIe and lauryl methacrylate. Examples of monomers of amide include Nt-butylacrylamide and Nt-octylacrylamide.

preferably used acrylic polymers obtained by the ethylenically unsaturated copolymerizing monomers containing hydrophilic groups, preferably of nonionic nature, such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and methacrylate, 2-hydroxypropyl.

The vinyl polymers may result from the homopolymerization or copolymerization of monomers chosen from vinyl esters, styrene or butadiene. Examples of vinyl esters include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate.

One can also use acrylic / silicone copolymers or even nitrocellulose / acrylic copolymers.

Polymers of natural origin, optionally modified, may be selected from shellac, sandarac gum, dammar the elemis, copals, cellulose derivatives, and mixtures thereof.

May also be mentioned the polymers resulting from the radical polymerization of one or more radical monomers inside and / or partially at the surface of preexisting particles of at least one polymer selected from the group consisting of polyurethanes, polyureas , polyesters, polyesteramides and / or alkyds. These polymers are generally called "hybrid polymers".

When an aqueous dispersion of polymer particles is used, the solids content of said aqueous dispersion may be of the order of 5-60% by weight, and preferably 30-50%.

The size of polymer particles in aqueous dispersion may be between 10 and 500 nm, and it is preferably between 20 and 150 nm, allowing the production of a film having a substantial gloss. However, one can use particle sizes up to one micron. Aqueous dispersions of film-forming polymer, one can use the acrylic dispersions sold under the names "Neocryl XK-90^® "" Neocryl A-1070^® "" Neocryl A-1090^® "" Neocryl BT-62^® "" Neocryl A-1079^® "And" A- 523 Neocryl^® "By the company Avecia-Neoresins," Dow Latex 432^® "By the company Dow Chemical," Daitosol 5000 AD^® "Or" Daitosol SJ 5000 "by the company Daito Kasey Kogyo; "Syntran 5760" by the company Interpolymer or aqueous polyurethane dispersions sold under the names "Neorez R-981^® "And" Neorez R-974^® "By Avecia-Neoresins," Avalure UR-405^® "" Avalure UR-410^® "" Avalure UR-425^® "" Avalure UR-450^® "," Sancure 875^® "," Sancure 861^® "," Sancure 878^® "And" Sancure 2060^® "By Goodrich," Impranil 85^® "By Bayer," Aquamere H-1511^® "HYDROMER by the company; sulphopolyesters sold under the brand name "Eastman AQ^® "By the company Eastman Chemical Products, vinyl dispersions, for instance" Mexomer. PAM "and mixtures thereof.

IV) water soluble polymers

In the case where the composition comprises an aqueous phase, the film-forming polymer may be a water soluble polymer. The water soluble polymer is solubilized in the aqueous phase of the composition.

Among the water-soluble film-forming polymers include the following cationic polymers:

(1) acrylic polymers or copolymers such as polyacrylates or polymethacrylates; copolymers of family (1) may further contain one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacétoneacrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower, acids acrylic or methacrylic acid or esters thereof, vinyllactams such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters. Thus, among these copolymers of family (1) include: copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl halide, such as that sold under the name HERCOFLOC by society HERCULES, the copolymer of acrylamide and methacrylic chloride cryloyloxyéthyltriméthylammonium described, for example, in EP-patent application 0809 76 and sold under the name Bina Quat P 100 by the company Ciba Geigy, the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate sold under the name Reten by the company HE RCULES, vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate, quaternized or non-quaternized, such as the products sold under the name "GAFQUAT" by ISP, such as for example "GAFQUAT 734" or "GAFQUAT 755", or alternatively the products designated "COPOLYMER 845, 958 and 937". These polymers are described in detail in French Patents 2,077,143 and 2,393,573, terpolymers of dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone such as the product sold under the name GAFFIX VC 713 by ISP, and - the copolymer vinylpyrrolidone / quaternized dimethylaminopropylmethacrylamide such as the product sold under the name "GAFQUAT HS 100" by ISP.

(2) quaternized polysaccharides described more particularly in US Patents 3,589,578 and US 4,031,307, such as guar gums containing cationic trialkylammonium groups. Such products are marketed in particular under the trade names Jaguar C13 S, Jaguar C 15 and Jaguar C 17 by Meyhall.

(3) copolymers of vinylpyrrolidone and quaternized vinylimidazole;

(4) chitosans or salts thereof;

(5) Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble monomer comprising a quaternary ammonium, and described in particular in US Patent 4,131,576, such as hydroalkyl celluloses like hydroxymethyl , hydroxyethyl or hydroxypropyl cellulose grafted in particular with a methacryloyloxyethyltrimethylammonium salt, methacrylamidopropyltrimethylammonium or dimethyl. The commercial products corresponding to this definition are more particularly the products sold under the name "CELQUAT L 200" and "CELQUAT H 100" by National Starch Company. Among the water-soluble film-forming polymers include the following amphoteric polymers:

(1) polymers resulting from the copolymerization of a monomer _, derived from a vinyl compound bearing a carboxylic group such as more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as, more particularly a dialkylaminoalkyl methacrylate and acrylate, and a dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds are described in US Patent No. 3 836 537. (2) polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen with an alkyl radical, b) at least one acidic comonomer containing one or more reactive carboxylic groups, and c) at least one basic comonomer such as esters, with primary amine substituents, secondary, tertiary and quaternary, of acrylic and methacrylic acids and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl sulfate or diethyl.

(3) crosslinked derivatives alkoylpolyaminoamides all or part of polyaminoamides.

(4) polymers comprising zwitterionic units. (5) the polymer derived from chitosan.

(6) polymers derived from the N-carboxyalkylation chitosan, such as N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under the name "EVALSAN" by the company Jan Dekker.

(7) copolymers of (C_rC₅) Alkyl vinyl ether / maleic anhydride partially modified by semiamidation with an N, N-dialkylaminoalkylamine, such as N, N-dimethylaminopropylamine or by semiesterification with an N, N-dialkanolamine. These copolymers can also contain other vinyl comonomers such as vinylcaprolactam.

The water-soluble film-forming polymers are preferably selected from the group consisting of: proteins such as proteins of plant origin, such as wheat or soy protein; animal proteins such as keratin, for example keratin hydrolysates and sulphonic keratins; anionic, cationic, amphoteric or nonionic chitin or chitosan; cellulosic polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methylcellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose, and quaternized derivatives of cellulose; acrylic polymers or copolymers such as polyacrylates or polymethacrylates; vinyl polymers, such as polyvinylpyrrolidones, copolymers of methyl vinyl ether and maleic anhydride, vinyl acetate copolymer and of crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate; - Copolymers of vinylpyrrolidone and caprolactam; polyvinyl alcohols; optionally modified polymers of natural origin, such as:. gum arabic, guar gum, xanthan derivatives, karaya gum; . alginates and carrageenans; . glycoaminoglycans, hyaluronic acid and its derivatives;

. shellac, sandarac gum, dammar the elemis, copals; . deoxyribonucleic acid;

. mucopolysaccharides, such as hyaluronic acid, chondroitin sulfate, and mixtures thereof.

These polymers will be used in particular if one wants a more or less appreciable removal of the film with water.

To improve the film-forming nature of an oily or aqueous polymer, it is possible to add to the polymer system a coalescing agent which is selected from the coalescing agents known.

According. one embodiment of the invention, the film-forming polymer few be chosen from polymers having a non-silicone organic skeleton grafted with monomers containing a polysiloxane. These polymers may be fat-soluble, fat-dispersible, soluble or dispersible in aqueous medium, as appropriate.

Polymers having a non-silicone organic skeleton grafted with monomers containing a polysiloxane are composed of a main organic chain formed from organic monomers not comprising silicone, on which is grafted, within said chain and also optionally on at least one of the ends thereof, at least one polysiloxane macromer. In what follows, it is understood that the term "polysiloxane macromer" means, as is generally accepted, any monomer containing a polysiloxane polymer chain in its structure.

The non-silicone organic monomers constituting the main chain of the grafted silicone polymer can be selected from the ethylenically unsaturated monomers can be polymerised by the free radical method, polymerizable monomers by polycondensation such as those forming polyamides, polyesters, polyurethanes, monomers opening cycle such as those of the oxazoline or caprolactone kind.

Polymers having a non-silicone organic skeleton grafted with monomers containing a polysiloxane according to the present invention can be obtained according to any method known to those skilled in the art, in particular by reaction between (i) a polysiloxane macromer starting correctly functionalized on the polysiloxane chain and (ii) one or more non-silicone organic compounds, themselves correctly functionalized with a function which is capable of reacting with the group or the functional groups (s) covered (s) by said silicone by forming a covalent bond; a classic example of such a reaction is the radical reaction between a vinyl group carried at one end of the silicone with a double bond of an ethylenically unsaturated monomer of the main chain.

Polymers having a non-silicone organic skeleton grafted with monomers containing a polysiloxane according to the invention are preferably selected from those described in US Patents 4,693,935, US 4,728,571 and US 4,972,037 and the patent applications EP A-0412704, EP-A-0412707, EP-A-0640105 and WO 95/00578. It relates to copolymers obtained by radical polymerization from monomers with ethylenic unsaturation and monomers having a terminal vinyl group, or copolymers obtained by the reaction of a polyolefin containing functionalized groups and a polysiloxane macromer having a terminal function reactive with said functionalized groups.

One particular family of grafted silicone polymers suitable for the implementation of the present invention consists of grafted silicone polymers containing a) from 0 to 98% by weight of at least one lipophilic monomer (A) of low lipophilic polarity ethylenic unsaturation, polymerizable by radical method; b) from 0 to 98% by weight of at least one polar hydrophilic monomer (B) containing ethylenic unsaturation, which is copolymerizable with the monomer or monomers of type (A); c) from 0.01 to 50% by weight of at least one polysiloxane macromer (C) of general formula:

X (Y)_notSi (R)₃._mZ_m (I) wherein:

X denotes a vinyl group copolymerizable with the monomers (A) and (B);

Y denotes a group having a divalent bond; R denotes hydrogen, alkyl or alkoxy -C₆, Aryl C₆-C₁₂;

Z denotes a monovalent polysiloxane unit having a number average molecular weight of at least 500; n is 0 or 1 and m is an integer from 1 to 3; the percentages being calculated relative to the total weight of monomers (A), (B) and (C).

These polymers have an average molecular weight ranging from 10 000 to 2 million, and preferably a glass transition temperature Tg or a crystalline melting temperature Tm of at least -20 ° C.

Examples of lipophilic monomers (A), there may be mentioned the esters in Cι-d₈ and acrylic or methacrylic acid; alcohol esters of C₁₂-C_thirty and methacrylic acid, styrene; polystyrene macromers; vinyl acetate; vinyl propionate; alpha-methylstyrene; tert-butylstyrene; butadiene; cyclo- hexadiene; cyclohexadiene [sic]; ethylene; propylene; vinyltoluene, esters of acrylic or methacrylic acid and 1, 1-dihydroperfluoroalkanols or of homologues thereof; esters of acrylic or methacrylic acid and omega- hydrofluoroalcanols; esters of acrylic or methacrylic acid and fluoroalkylsulfonamidoalcools; esters of acrylic or methacrylic acid and fluoroalkylalcools; esters of acrylic or methacrylic acid and alcohol-fluoroethers; or mixtures thereof. The monomers (A) are preferred selected from the group consisting of methacrylate, n-butyl methacrylate, isobutyl acrylate, t-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methyl methacrylate, 2- (N- méthylperfluorooctanesulfonamido) ethyl acrylate, 2- (N-butylperfluorooctanesulfona- mido) ethyl, or mixtures thereof. Examples of monomers (B) polar, there may be mentioned acrylic acid, methacrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, (meth) acrylamide, Nt-butylacrylamide , maleic acid, maleic anhydride and hemiesters thereof, (meth) acrylates, diallyldimethylammonium chloride, vinylpyrrolidone, vinyl ethers, maleimides, vinylpyridine, vinylimidazole, and heterocyclic vinyl polar compounds, styrene sulphonate, allyl alcohol, vinyl alcohol, vinylcaprolactam or mixtures thereof. The monomers (B) are preferably selected from the group consisting of acrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinylpyrrolidone, and mixtures thereof.

especially be mentioned the product KP 561 or KP 562 sold by Shin Etsu as the monomer (A) and chosen from the esters of C ^ -C ^ and methacrylic acid.

polysiloxane macromers (C) of formula (I) are preferably chosen from those corresponding to the general formula (II):

CHtf≈CR * - CO &lt;CH₂) - (0) -SKR - &lt;- 0 ~ If -) - &lt;(, |)

CH_at wherein: R¹ is hydrogen or -COOH (preferably hydrogen);

R² is hydrogen, methyl or -CH₂COOH (preferably methyl);

R³ is alkyl, alkoxy or alkylamino CC₆, Aryl C₆-C₁₂ or hydroxyl (preferably methyl);

R⁴ is alkyl, alkoxy or alkylamino, C_rC₆, Aryl C₆-C₁₂ or hydroxyl (preferably methyl); q is an integer ranging from 2 to 6 (preferably 3); p is 0 or 1; r is an integer from 5 to 700; m is an integer from 1 to 3 (preferably 1). preferably macromers polysiloxane of the formula:

<img id="imgf000042_0001" he="20" wi="95" file="imgf000042_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> n being a number ranging from 5 to 700 and I being an integer between 0 and 3.

An embodiment of the invention is the use of a copolymer capable of being obtained by radical polymerization starting with a monomer mixture consisting of: a) 60% by weight of tert-butyl acrylate; b) 20% by weight of acrylic acid; c) 20% by weight of silicone macromer of formula:

Hf JL₀_ ⁽"Y" Si - O- (CH_jJI- CH,

O *. CH_j ' <img id="imgf000043_0001" he="21" wi="22" file="imgf000043_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> n being a number ranging from 5 to 700 and I being an integer between 0 and 3, the weight percentages being calculated relative to the total weight of the monomers.

Another particular embodiment of the invention is the use of a copolymer capable of being obtained by radical polymerization starting with a monomer mixture consisting of: a) 80% by weight of tert-butyl acrylate ; b) 20% by weight of silicone macromer of formula:

O CH, CH, CH, i ³ i

H₂C ^• O - (CH₂)₃- • if Si-O Si - (CR_&gt;) 1 - CH

CH_at in. CH, CH,

n being a number ranging from 5 to 700 and I being an integer between 0 and 3, the weight percentages being calculated relative to the total weight of the monomers.

Another particular family of grafted silicone polymers with a non-silicone organic skeleton suitable for an implementation of the present invention consists of grafted silicone copolymers capable of being obtained by reactive extrusion of a polysiloxane macromer terminal function on a reactive polymer of the polyolefin type comprising reactive groups capable of reacting with the terminal function of the polysiloxane macromer to form a covalent bond allowing grafting of the silicone to the main chain of the polyolefin. These polymers and their method of preparation are described in the patent application WO 95/00578.

Reactive polyolefins are preferably selected from polyethylenes or polymers of monomers derived from ethylene, such as propylene, styrene, alkylstyrene, butylene, butadiene, (meth) acrylates, vinyl esters or equivalents, comprising reactive functions capable of reacting with the terminal function of the polysiloxane macromer. They are more particularly selected from ethylene or of ethylene derivatives and copolymers the monomers chosen from those comprising a carboxylic function such as (meth) acryiique; those comprising an acid anhydride function, such as anhydride of maleic acid; those comprising an acid chloride function such as the chloride of (meth) acrylic acid; those comprising an ester function such as the esters of (meth) acrylic acid; and those comprising an isocyanate function.

Silicone macromers are preferably chosen from polysiloxanes comprising a functionalized group, at the end of the polysiloxane chain or close to the end of said chain, chosen from the group consisting of alcohols, thiols, epoxy , primary and secondary amines, especially from those corresponding to the general formula: T- (CH₂)₆-Si - [- (OSiR⁵R⁶)_t-R⁷]_there (III) wherein T is selected from the group consisting of NH₂, NHRN, an epoxy, OH, SH; R⁵, R⁶, R⁷ and RN independently denote alkyl, Cι-C₆, Phenyl, benzyl or alkylphenyl C₆-C₁₂, Hydrogen; s is a number ranging from 2-00 [sic], t is a number ranging from 0 to 1000 and y is a number from 1 to 3. They have a number average molecular weight of preferably from 5,000 to 300,000, more preferably from 8000 to 200 000, more especially from 9000 to 40 000.

According to a preferred embodiment, the film-forming polymer may be purchased from the Minnesota Mining and Manufacturing Company under the trade names of polymers "Silicone Plus". For example, poly (methacrylate methyl isobutyl co-FOSEA) -g-poly (dimethylsiloxane) is sold under the trade name SA 70-5 IBMMF.

According to another preferred form of the invention, the film-forming polymer is chosen from silicone polymers grafted with non-silicone organic monomers. These polymers may be liposoluble, lipodispersible, soluble or dispersible in aqueous medium, as appropriate.

Said polymer or said silicone polymer (s) grafted (s) containing a polysiloxane skeleton grafted with non-silicone organic monomers containing a main silicone chain (or polysiloxane (/ SiO)_not) On which is grafted, with within said chain and optionally at one at least of its ends, at least one organic group not comprising silicone.

Polymers containing a polysiloxane skeleton grafted with non-silicone organic monomers of the invention may be existing commercial products or can be obtained by any means known to those skilled in the art, in particular by reaction between ( i) a silicone departure correctly functionalized on one or more of these silicon atoms and (ii) a non-silicone organic compound itself correctly functionalized with a function which is capable of reacting with the group or the functional groups (s) carried (s) by said silicone by forming a covalent bond; a classic example of such a reaction is the hydrosilylation reaction between groups / Si-H groups and vinyl groups CH₂= CH-, or the reaction between -SH thio-functional groups with these same vinyl groups.

Examples of polymers containing a polysiloxane skeleton grafted with non-suitable silicone organic monomers to an implementation of the present invention and their specific method of preparation are described in particular in patent applications EP-A-0 582 152, WO 93/23009 and WO 95/03776, whose teachings are completely included in this description by way of non-limiting references.

According to a particularly preferred embodiment of the present invention, the silicone polymer, containing a polysiloxane skeleton grafted with non-silicone organic monomers, implemented, consists of the result of radical copolymerization between, on the one hand, to least one anionic non-silicone organic monomer with ethylenic unsaturation and / or one hydrophobic non-silicone organic monomer with ethylenic unsaturation and, on the other, a silicone having in its chain at least one functional group, and preferably several, capable of reacting with said ethylenic unsaturations of said non-silicone monomers, forming a covalent bond, in particular thio-functional groups.

According to the present invention, said anionic monomers containing ethylenic unsaturation are preferably selected, alone or as mixtures, from unsaturated carboxylic acids, linear or branched, optionally partially or totally neutralized in the form of a salt, this or these acid (s) carboxylic acid (s) unsaturated (s) being more particularly acrylic acid, methacrylic acid, maleic acid, itaconic, fumaric acid and crotonic acid. Suitable salts are in particular alkali metal salts, alkaline earth and ammonium salts. Note that, similarly, in the final grafted silicone polymer, the organic group of anionic nature which is composed of the result of the (homo) radical of at least one anionic monomer of unsaturated carboxylic acid type polymerization may be, after reaction , post-neutralized with a base (soda, ammonia, etc.) to bring it into the form of a salt.

According to the present invention, the hydrophobic monomers containing ethylenic unsaturation are preferably selected, alone or as a mixture, from acrylic acid esters of alkanols and / or methacrylic acid esters of alkanols. The alkanols are preferably DC_thirty and more particularly to DC₂₂. Preferred monomers are selected from the group consisting of (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) - acrylate, isopentyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylate, t-butyl (meth) acrylate, tridecyl and (meth) acrylate, or mixtures thereof.

One family of silicone polymers containing a polysiloxane skeleton grafted with non-silicone organic monomers, particularly suitable for the implementation of the present invention consists of silicone polymers comprising in their structure the unit of formula IV below:

<img id="imgf000046_0001" he="17" wi="83" file="imgf000046_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein G ^ identical or different radicals, represent hydrogen or an alkyl radical -C₁₀Or a phenyl radical; the radicals G₂, Identical or different, represent represents [sic] an alkylene group C_rC₁₀ ; G₃ represents a polymer residue resulting from the (homo) polymerization of at least one anionic monomer containing ethylenic unsaturation; G₄ represents a polymer residue resulting from the (homo) polymerization of at least one monomer of at least one hydrophobic monomer [sic] with ethylene unsaturation; m and n are equal to 0 or 1; a is an integer ranging from 0 to 50; b is an integer which may be between 10 and 350, c is an integer ranging from 0 to 50; provided that one of the parameters a and c is other than 0.

The unit of formula (IV) of the text above preferably has at least one, and more preferably all, of the following characteristics: Gi radicals denote an alkyl radical, preferably a methyl radical; n is not zero, and the radicals G₂ represent a divalent C_rC₃, Preferably a propylene radical; - G₃ represents a polymer radical resulting from the (homo) polymerization of at least one monomer of the ethylenically unsaturated carboxylic acid, preferably acrylic acid and / or methacrylic acid;

G represents a polymer radical resulting from the (homo) polymerization of at least one monomer of the (meth) acrylate Cio C, preferably (meth) acrylate or methyl.

Examples of silicone polymers corresponding to formula (IV) are in particular polydimethylsiloxane (PDMS) onto which are grafted, via a secondary link of thiopropylene type, mixed polymer units of poly (meth) acrylic acid and poly (meth) acrylate.

Other examples of silicone polymers corresponding to formula (IV) are in particular polydimethylsiloxane (PDMS) onto which are grafted, via a secondary link of thiopropylene type, polymer units of the poly (meth) acrylate isobutyl.

Such polymers include polymers comprising at least one group of formula:

<img id="imgf000047_0001" he="52" wi="107" file="imgf000047_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein a, b and c can be identical or different, are each a number ranging from 1 to 100 000; and the terminal groups, may be identical or different, are each chosen from linear alkyl groups CC₂₀, The alkyl groups branched chain C₃-C₂₀, The aryl groups in C₃-C₂₀, Linear alkoxy groups, C_rC₂₀ and branched alkoxy groups, C₃-C₂₀.

Such polymers are disclosed in, U.S. Patent No. 4,972,037, 5,061,481, 5,209,924, 5,849,275 and 6,033,650, and WO 93/23446 and WO 95/06078.

Another family of silicone polymers containing a polysiloxane skeleton grafted with non-silicone organic monomers particularly well suited to implementation of the present invention, is constituted by silicone polymers comprising in their structure the unit of formula (V) below -Dessous:

<img id="imgf000048_0001" he="26" wi="100" file="imgf000048_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein Gi and G radicals₂ have the same meaning as above; G₅ represents a polymer residue resulting from the (homo) polymerization of at least one monomer of at least one hydrophobic monomer [sic] with ethylenic unsaturation or copolymerization of at least one anionic ethylenically unsaturated monomer and at least a hydrophobic monomer containing ethylenic unsaturation; n is 0 or 1; a is an integer ranging from 0 to 50; b is an integer which may be between 10 and 350; provided that a is not 0.

The unit of formula (V) in the above text preferably has at least one, and more preferably all, of the following characteristics: the radicals G_\ denote an alkyl radical, preferably a methyl radical; n is not zero, and the radicals G₂ represent a divalent C_rC₃, Preferably one. propylene radical.

The molecular weight of silicone polymers containing a polysiloxane skeleton grafted with non-silicone organic monomers of the invention preferably ranges from about 10 000 to 1 000 000, and more preferably from about 10 000 to 100 000.

The composition may contain from 2 to 60% by weight, preferably 5 to 60%, preferably 2 to 30% by weight of dry matter of film-forming polymer. More generally, total amount of polymer must be sufficient to form on the skin and / or lips a cohesive film capable of following the movements of the skin and / or lips without becoming detached or cracking.

When the polymer has a too high glass transition temperature for the desired use, a plasticizer may associate so as to lower this temperature of the mixture used. The plasticizer may be chosen from the plasticizers usually used in the field of application, and especially from compounds which may be solvents for the polymer.

The composition according to the invention may comprise a hydrophilic medium comprising water or a mixture of water and solvent (s) organic (s) hydrophilic (s) such as alcohols and especially linear or branched lower monoalcohols having 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, and polyols such as glycerol, diglycerol, propylene glycol, sorbitol, pentylene glycol and polyethylene glycols, or alternatively of ethers of C₂ aldehydes and C₂-C₄ hydrophilic.

The water or the mixture of water and hydrophilic organic solvents may be present in the composition according to the invention in a content ranging from 0.1% to 99% by weight, relative to the total weight of the composition, and preferably from 10% to 80% by weight.

The composition according to the invention may contain emulsifying surfactants, present in particular in a proportion ranging from 2 to 30% by weight relative to the total weight of the composition and better still from 5% to 15%. These surfactants may be chosen from anionic or nonionic surfactants. We can refer to the document "Encyclopedia of Chemical Technology, Kirk-Othmer", volume 22, p.333- 432, 3rd edition, 1979, Wiley, for the definition of the properties and functions (emulsifying) of surfactants, in particular p .347-377 of this reference, for the anionic and nonionic surfactants.

The surfactants preferably used in the composition according to the invention are chosen:

- Among the nonionic surfactants: fatty acids, fatty alcohols, polyethoxylated or polyglycerolated fatty alcohols such as stearyl or cetylstearyl alcohols, fatty acid esters of sucrose, alkyl glucose esters, in particular fatty esters of C-ι-C₆ polyoxyethylenated alkyl glucose, and mixtures thereof. - From anionic surfactants: fatty acids C16-C30 neutralized with amines, aqueous ammonia or alkaline salts, and mixtures thereof.

According to one embodiment, is used Surfactants which allow to obtain an oil-in-water or wax-in-water emulsion.

The composition according to the invention comprises a cosmetically acceptable organic liquid medium (tolerance, toxicology and feel).

According to a particularly preferred embodiment, the organic liquid medium of the composition. contains at least one organic solvent, which is the or one of the polymerization solvents of the block polymer as described above. Advantageously, said organic solvent is the majority liquid by weight in the organic liquid medium of the cosmetic composition.

According to one embodiment, the organic solvent medium comprises fatty bodies liquid at ambient temperature (25 ° C in general) known as oils. These liquid fatty substances may be of animal, plant, mineral or synthetic. As oils used in the invention include: hydrocarbon oils of animal origin such as perhydrosqualene; hydrocarbon-based plant oils such as liquid triglycerides of fatty acids of 4 to 10 carbon atoms such as triglycerides of heptanoic or octanoic acid, or alternatively sunflower oil, corn oil, soybean oil, grapeseed oil, sesame oil, apricot, macadamia, castor oil, avocado oil, triglycerides of caprylic / capric acids, jojoba oil, shea butter; linear or branched hydrocarbons of mineral or synthetic origin such as liquid paraffins and derivatives thereof, petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam; the synthetic esters and ethers, especially of fatty acids such as purcellin oil, isopropyl myristate, 2-ethyl-hexyl stearate, 2-octyl-dodecyl erucate octyl-2-octyldodecyl erucate, isostearyl isostearate; hydroxy esters such as isostearyl lactate, octyl, octyldodecyl hydroxystearate, diisostearylmalate, triisocetyl citrate heptanoates, octanoates decanoates of fatty alcohols; polyol esters such as propylene glycol dioctanoate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate; and pentaerythritol esters; fatty alcohols having 12 to 26 carbon atoms such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol or 2-undecylpentadecanol, oleyl alcohol; partially hydrocarbon-based fluoro oils and / or silicone; silicone oils such as polydimethylsiloxanes (PDMS), volatile or not, linear or cyclic, such as cyclomethicones, dimethicones, optionally comprising a phenyl group, such as phenyltrimethicones, phenyltrimethylsiloxydiphenylsiloxanes siloxanes, diphenylmethyldimethyltrisiloxanes, diphenyl dimethicones, phenyl dimethicone, polymethylphenylsiloxanes; mixtures thereof.

These oils may be present in a content ranging from 0.01 to 90%, and preferably from 0.1 to 85% by weight, relative to the total weight of the composition.

The organic liquid medium of the composition according to the invention may also comprise one or more organic solvents, cosmetically acceptable (acceptable tolerance, toxicology and feel).

These solvents may be generally present in a content ranging from 0.1 to 90%, more preferably from 10 to 90% by weight, relative to the total weight of the composition and better still from 30 to 90%.

As solvents used in the composition of the invention include, besides the hydrophilic organic solvents mentioned above, ketones that are liquid at room temperature such as methyl ethyl ketone, diisobutyl ketone, isophorone, cyclohexanone or acetone; liquid propylene glycol ethers at room temperature, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, mono-n-butyl ether of dipropylene glycol; short-chain esters (containing from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate isopentyl; ethers that are liquid at room temperature such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes that are liquid at room temperature, such as decane, heptane, dodecane, isododecane or cyclohexane; liquid aromatic cyclic compounds at room temperature such as toluene and xylene; aldehydes that are liquid at room temperature, such as benzaldehyde and acetaldehyde, and mixtures thereof.

The composition according to the invention may comprise at least one wax. By wax in the sense of the present invention, means a lipophilic compound that is solid at room temperature (25 ° C), with reversible solid / liquid reversible, having a melting point up to 30 ° C up until to 120 ° C. The melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC 30 by the company Mettler.

The waxes can be hydrocarbon, fluorinated and / or silicone and may be of plant, mineral, animal and / or synthetic. In particular, the waxes have a melting point greater than 25 ° C and greater than 45 ° C. As waxes used in the composition of the invention include beeswax, carnauba wax or candelilla wax, paraffin, microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene waxes or Fischer-Tropsch, silicone waxes such as alkyl or aikoxy dimethicones containing from 16 to 45 carbon atoms.

The gums are generally polydimethylsiloxanes (PDMS) with high molecular weight or cellulose gums or polysaccharides. The pasty substances are generally hydrocarbon compounds such as lanolin and derivatives thereof, or PDMS.

The nature and quantity of solid fats depend on the mechanical properties and textures. As a guide, the composition may contain from 0 to 50% by weight of waxes, relative to the total weight of the composition and better still from 1 to 30% by weight. The polymer may be associated with one or auxiliary film-forming agents. Such a film-forming agent can be chosen from all the compounds known to the art as being capable of fulfilling the desired function, and may be chosen from plasticizers and coalescing agents.

The composition according to the invention may further comprise one or more dyestuffs chosen from water-soluble dyes and pulverulent coloring materials such as pigments, pearlescent agents and glitter well known in the art. The dyestuffs may be present in the composition in a content ranging from 0.01% to 50% by weight, based on the weight of the composition, preferably from 0.01% to 30% by weight.

Pigments should be understood particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition.

Pearlescent agents should be understood to mean iridescent particles of any form, especially produced by certain mollusks in their shell or synthesized. The pigments can be white or colored, inorganic and / or organic. These include, among inorganic pigments, titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxide, and also zinc oxide, iron oxide (black, yellow or red) or chromium, violet manganese, ultramarine blue, chromium hydrate and ferric blue, and metal powders such as aluminum powder, copper powder. Among the organic pigments, carbon black include, type of the D &amp; C pigments, and lakes based on cochineal carmine, barium, strontium, calcium and aluminum.

It may also be made of effect pigments, such as particles comprising an organic or inorganic substrate, natural or synthetic, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, the said substrate being uncoated or coated with metallic substances such as aluminum, gold, silver, platinum, copper, bronze, or metal oxides such as titanium dioxide, iron oxide, chromium oxide and mixtures thereof.

The pearlescent pigments can be chosen from white pearlescent pigments such as mica coated with titanium or with bismuth oxychloride, colored pearlescent pigments such as titanium mica coated with iron oxides, titanium mica coated especially with blue iron or chromium oxide, titanium mica coated with an organic pigment of the abovementioned type, and pearlescent pigments based on bismuth oxychloride. . One can also use interference pigments, in particular liquid crystal or multilayer.

Water-soluble dyes are for example beetroot juice, methylene blue.

The composition according to the invention may further comprise one or more fillers, especially in a content ranging from 0.01% to 50% by weight, based on the total weight of the composition, preferably from 0.01% to 30 % in weight. By fillers are meant particles of any shape, colorless or white, inorganic or synthetic, insoluble in the medium of the composition irrespective of the temperature at which the composition is manufactured. These fillers serve especially to modify the rheology or texture of the composition. The fillers may be mineral or organic of any shape, platelet, spherical or oblong, whatever the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.). There may be mentioned talc, mica, silica, kaolin, polyamide (Nylon®) (Orgasol® from Atochem), poly-β- alanine and polyethylene, tetrafluoroethylene polymer powders (Teflon®), lauroyl lysine, starch, boron nitride, hollow polymer microspheres such as those of polyvinylidene chloride / acrylonitrile, Expancel® (Nobel Industrie), acrylic acid copolymers (Polytrap® from Dow Corning) and microbeads of silicone resin ( Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydrogen carbonate, hydroxyapatite, hollow silica microspheres (silica Beads® of Maprecos), glass microcapsules or ceramic, and metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example zinc stearate, magnesium or lithium laurate zinc, magnesium myristate.

The composition according to the invention may especially be in stick form, suspension, dispersion, solution, gel, emulsion, including oil-in-water emulsion (O / W) or water-in-oil ( W / O) or multiple (W / O / W or polyol / O / W or O / W / O), as a cream, paste, foam, dispersion of vesicles, especially of ionic or nonionic lipids, biphase or multiphase lotion, a spray, a powder, a paste, especially a soft paste (in particular paste having a dynamic viscosity at 25 ° C of the order of 0.1 to 40 Pa.s at a shear rate of 200 s^"1After 10 minutes geometry measurement cone / plate). The composition may be anhydrous, for example it may be an anhydrous paste.

The skilled person may select the appropriate dosage form and its method of preparation, on the basis of his general knowledge, taking into account both the nature of the constituents used, especially their solubility in the support, and secondly to the application envisaged for the composition.

The composition according to the invention may be a makeup composition such as products for the complexion (foundations), blushers or eyelids, red lipsticks, concealer products, blushers, mascaras , eyeliners, eyebrow makeup products, lip pencils or eyes, nail products, such as nail varnishes, body makeup products or hair makeup product (mascara or hair spray). The composition according to the invention may also be a care of body and facial skin, in particular a sunscreen or skin coloring (such as a self-tanning).

The composition according to the invention can also be a hair product, especially for holding the hairstyle or shaping the hair. The hair compositions are preferably shampoos, gels, hair setting lotions, blow-drying lotions, fixing and styling compositions such as lacquers or sprays.

According to one embodiment, the invention relates to a composition for coating keratin fibers (such as the eyelashes, eyebrows, hair) comprising an organic liquid medium, at least one aqueous phase and at least one ethylenic linear block polymer and forming a dispersion of film-forming polymer particles as described above.

Advantageously, the film-forming polymer dispersible in water is chosen from polyurethanes, polyurethane-acrylics, polyacrylics, polyesters, (meth) acrylic acid, polyvinylpyrrolidone, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea / polyurethanes, and mixtures thereof as defined above.

Advantageously, the composition comprises at least one second film-forming agent selected from water-soluble polymer such as cationic cellulose derivatives and / or optionally modified polymers of natural origin such as gum arabic. Preferably, said composition comprises a wax and more preferably, it comprises a surfactant.

Such a composition may be in various forms: for example, in the form of emulsions multiphase wax-in-water or water-in-wax, aqueous or anhydrous dispersions.

Advantageously, the composition is a composition for coating the eyelashes or mascara.

The present invention also relates to a cosmetic assembly comprising: - a container delimiting at least one compartment, said container being closed by a closing member; and - A composition as described above disposed within said compartment.

The container can be in any suitable form. It may especially be in the form of a bottle, a tube, a jar, a case, a box, a sachet or a carton.

The closing member may be in the form of a removable stopper, a lid, a cover, a tear-off strip or a capsule, especially of the type comprising a body fixed to the container and a cap articulated on the body. It may also be in the form of a member ensuring the selective closure of the container, especially a pump, a valve or a flap valve.

The container may be combined with an applicator, especially in the form of a brush comprising an arrangement of bristles maintained by a twisted wire. Such a twisted brush is described especially in patent US 4 887 622. It may also be in the form of a comb comprising a plurality of application members, obtained especially by molding. Such combs are described for example in patent FR 2 796 529. The applicator may be in the form of a brush, as described for example in patent FR 2 722 380. The applicator may be in the form of a block of foam or of elastomer, a felt or a spatula. The applicator may be free (tuft or sponge) or securely fastened to a rod borne by the closing member, as described for example in US Patent 5 492 426. The applicator may be secured to the receptacle, as described for example FR 2761959.

The product may be contained directly in the container, or indirectly. For example, the product may be arranged on an impregnated support, especially in the form of a wipe or a pad, and arranged (individually or in plurality) in a box or in a sachet. Such a support incorporating the product is described for example in patent application WO 01/03538.

The closing member may be coupled to the container by screwing. Alternatively, the coupling between the closing member and the container is done other than by screwing, especially via a bayonet mechanism, by snap-fastening, gripping, welding, bonding or by magnetic attraction. "Snapping" means in particular any system involving the crossing of a bead or cord of material by elastic deformation of a portion, including the closure, followed by return to position elastically unconstrained said portion after the crossing of the bead or cord.

The container may be at least partly made of thermoplastic material. Examples of thermoplastic materials include polypropylene or polyethylene.

Alternatively, the container is made of non-thermoplastic material, especially glass or metal (or alloy).

The container may have rigid walls or deformable walls, especially in form of a tube or a tubular bottle.

The container may comprise means for causing or facilitating the distribution of the composition. For example, the container may have deformable walls so as to cause the output of the composition in response to an excess pressure inside the container, this positive pressure being caused by elastic (or non-elastic) squeezing of the container walls . Alternatively, especially when the product is in the form of a stick, the latter can be driven by a piston mechanism. Always in the case of a stick, especially of makeup product (lipstick, foundation, etc.), the container may comprise a mechanism, especially a rack, or a threaded rod, or with a helical ramp, and capable of moving a stick in the direction of the opening. Such a mechanism is described for example in FR 2806273 or in patent FR 2 775 566. Such a mechanism for a liquid product is described in FR 2,727,609.

The container may consist of a carton with a base delimiting at least one housing containing the composition, and a lid, especially articulated on the base, and capable of covering at least partially said bottom. Such a case is described for example in application WO 03/018423 or in patent FR 2 791 042.

The container may be equipped with a drainer arranged in the vicinity of the container opening. Such a drainer makes it possible to wipe the applicator and possibly the rod to which it may be secured. Such a drainer is described for example in FR 2792618.

The composition may be at atmospheric pressure inside the container (at room temperature) or pressurized, especially by means of a propellent gas (aerosol). In the latter case, the container is equipped with a valve (of the type used for aerosols).

The content of the patents or patent applications mentioned above are incorporated by reference in the present application.

The following examples are not limited to illustrate the compositions according to the invention.

Example 4: Red liquid lèyres

<img id="imgf000058_0001" he="90" wi="151" file="imgf000058_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

On the other hand, its implementation is effortless with a foam applicator and leads to a homogeneous deposit of good behavior.

Example 5: Anti-sun composition

<img id="imgf000058_0002" he="30" wi="110" file="imgf000058_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" /><img id="imgf000059_0001" he="172" wi="110" file="imgf000059_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

Example 6-11: Mascaras emulsions

The following mascara compositions according to the invention and the prior art were prepared:

The composition of Example 6 according to the prior art, not include block polymer or aqueous dispersion of film-forming polymer particles.

The composition of Example 10 comprises an aqueous dispersion of film-forming polymer particles but no block polymer.

The compositions of Examples 7 to 9 and 11 according to the invention include a block polymer and an aqueous dispersion of film-forming polymer particles. <img id="imgf000060_0001" he="117" wi="171" file="imgf000060_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

* AM: active material

Each composition was measured dry, in vitro and load holding, using the methods described below.

The load is measured in vitro by gravimetry on 10 Caucasian hair curves of specimens (30 cm 1 long hair spread over a distance of 1cm).

The sample is made up by making 3x10 mascara passages spaced 2 minutes with product recovery between each set of 10.

The specimen is dried 10 min at room temperature and weighed.

This measurement is performed on specimens 15 6 The charge is actually the amount of material deposited on the specimen = mass makeup test - mass naked specimen.

The average charge is the average of measurements made on 6 specimens. The solids content, ie the non-volatile matter content or solids content of the compositions is measured on a Mettler Toledo HG 53 (Halogen Moisture Analyzer). A mascara sample (2-3 g) is placed on an aluminum dish and undergoes a temperature of 120 ° C for 60 minutes. Measuring the dry extract is to monitor the mass of the sample versus time .The final solids content is the percentage of the final weight (after 60 min) compared to the initial mass: ES = (final weight / initial weight) X 100.

Holding the film formed by the composition of the invention is evaluated by measuring the water resistance, a function of time ,, of a composition film spread on a glass plate and subjected to an aqueous medium by stirring . The protocol is as follows: At room temperature (25 ° C) was spread a layer of composition of 300 .mu.m thickness (before drying) of a surface of 9 cm. X 9 cm on a glass plate with a surface of 10 cm X 10 cm, then dried for 24 hours at 30 ° C and 50% relative humidity. After drying, the plate is placed in a crystallizer with a diameter of 19 cm and a capacity of 2 liters filled with one liter of water placed on a heating magnetic stirrer sold under the name RCT basic by the company IKA labor technik. then placed on the film a smooth cylindrical bar magnet PTFE (6 cm long, 1 cm diameter). stirring rate is adjusted to 5. The water temperature is controlled using a thermometer at temperature of 20 ° C or 40 ° C. At time t₀ = 0, we start the agitation. the time t is measured (in minutes) after which the film begins to detach or come off the plate or when there is a hole the size of the magnetic stirring bar, that is to say, when the hole has a diameter of 6 cm. the water resistance of the film is measured at time t.

We obtain the following results

<img id="imgf000061_0001" he="54" wi="162" file="imgf000061_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" /> It is found that the compositions according to the invention of Examples 7 to 9 and 11 comprising combining an aqueous dispersion of film-forming polymer particles and a polymer block have good performance, better than the composition of Example 10 which does not include a block polymer. In addition, the compositions of the invention allow a thick eyelash makeup because they have a dry and high load values ​​in vitro.

Example 12: Waterproof mascara

the following mascara was prepared according to the invention:

Carnauba wax 4.7

Beeswax 8.2

rice bran wax 2.2

Hectorite modified ( "Bentone 38V^® "5.5 of Elementis

Paraffin wax 2.2

talc 1

Copolymer of vinyl acetate / allyl stérarate 6.7

(Mexomere PQ from Chimex)

Block polymer of Example 1, 10

polyvinyl laurate (PP Mexomere the company 0.7

CHIMEX)

Sulfopolyester (Eastman AQ 55S from Eastman) 0.1

preservatives 0.2

propylene carbonate 1, 8

water 7

pigments 5.2

Isododecane qs 100

Was measured dry, in vitro and load holding, according to measurement method described above in the description.

The following results were obtained <img id="imgf000063_0001" he="23" wi="117" file="imgf000063_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

This mascara has a good performance while having a good thickening effect (charging) of the eyelashes.